Clarification and purification of industrial liquors



P carton rnuca'rlols or I moose arduous Walter ammo, Woodbridge, and. Sandiord 8.

. Cole, Metuchen, N.

,assignors to National Lead Company, New YM'QQN- E, a corporation of New .iersey No Drawing.- Application April as, loll.

serial No. sadist- This invention relates to the'clarification and purification of industrial liquors. It has particular reference to solutions containing strong inorganic acids and still more particularly to solutions obtained in the sulfuric acid processes for the manufacture of titanium dioxide pigments a certain amount of unattacked ore as well as other insoluble matter mainly consisting of colloidal and near colloidal particles of titanium compounds, siliceous material and silicates.

. (cl. Mil-425i i the suspended insoluble colloidal residue in suliuric acid solutions containing titanium and iron is most effective when applied to solutions of a not too high specific gravity, i. e., the degree of of filtration are such as clarification can be carsubsequent limviation of the-digestion product a considerable portion of the insoluble material 1 remainse in coilloldal suspension and must be coagulated before it can be removed from the solution by. settling or filtration.

The problem of removing colloidal unfilterable ral' matter from sulfuric acid-ilmenite solutions and other similar solutions has been the quence, of these extensive researches a number ofdlfierentpurification processes have been; disclosed in the prior art.-- All thes'eprocesses deal with the removal of the suspended unfilterable material by coagulation brought about'by addingfto the solution or causing to be formed therein an agent or a compound having'a polarity op-=" l osite to that of the suspended material, fol- ,acid-illnenite solutions, disclosed in the prior art, -is the coagulation of the suspended matter by 3 the addition. of an organic colloid, such as glue.

subject oi considerable research. As a conse-- flocculation, the rate of settling and the rate ried out in an efiective and economical manner only when operating with solutions of a specific gravity below 1.500, preferably not above 1.475.

It is necessary when coagulating with glue to add about one part of dry glue by weight to about 1000 parts of solution.

It has also been observed when the clarifica tion is carried out with the aid of insoluble metal sulfides, for example, antimony sulfide, according to known methods, that'it is possible to operate with sulfate solutions of higher concentrations than is possible when using glue as a coagulant. Solutions of specific gravities of from about 1.550 to about 1.570 may be successfully clarified by this method.

The advantage to the industry inherent in the latter clarification method is obvious in that the subsequent crystallizationof excess ferrous sulproc- Another known process which is eiiective in the I clarification of industrial liquors, and which is especially adaptable for the clarification of reduced, crude solutions of ilmenite in sulfuric acid, is the coagulation of the suspended residue with an insoluble metal sulfide, such as for example, antimony sulfide or coppersulfide, which is formed in situ, i. e., in thesolution to be clarified. The negatively charged particles of the metal sulfide and the positively charged colloidal suspended matter are mutually neutralized causin: a coagulation or flocculation to occur. In this process itis convenient to have the metal in question" in the solution to be clarified and to add a solution of a soluble sulfide, preferably alkali fate and concentration steps may be carried out more effectively and with more economy than is possible when operating with solutions of lower concentrations.

One procedure of the titanium dioxide industry for the separation of the coagulatedresidue from sulfate solutions is to allow the flocs to settle'out in a continuous operation in a settling.

tank. The more or less clarified "over-flow from the tank is in a subsequent step freed of remaining unsettled coagulated matter by filtration, the underfiow containing-practically all of the coagulated residue being separately processed for the separation of the liquid irom the solids before being recirculated in the solution-producing system. The overfiow" from such a continuous settlin system. which'as alreadyv pointed out stillco'ntains sulfide, in, amounts sufiicient for the precipitanon of the insoluble metal sulfide.

' It hasheen observed that the use of organic colloids, su'chas common glue, as a coagulant for r a certain amount of unsettledmatter, the com-' plete removal of which by gravitational settling,

would :be altogether teatime-consuming for an emcient operation, is customarily subjected to a filtration operation, preferably in a filter press by which it is possible rapidly to produce a completely clarified solution, and it is in this filtration step that the eificiency of the whole clarification system to-a great extent depends.

When the rate of flow, from the filter press because of blinding oi the filter medium slows down below a point where productionno longer can be maintained, it becomes necessary to shut the press down for renewal of the filter aid which is used in conjunction with the usual filter media. The time which elapses between necessary shut-downs for removal of the filter aid generally in the form of a precoat is designated as a filter-cycle in the industry.

The shut-down of the filter press interrupts production, is labor-consuming and otherwise expensive. It will therefore be recognized that it is desirable from a standpoint of uninterrupted production and economy to maintain the rate of flow of filtered liquor for the longest possible time, i. e., to be able to operate with long filtercycles.

The "underilow from the settling tank. containing substantially all of the coagulated materiahhereafter referred to as mud, is treated in as possible of the titanium dioxide containing mud" to the digestion system for a more complete recovery of the titanium values, and. that the more efficient the clarification system operates the more of the "mud can be circulated therein without enlarging the facilities.

While clarification of sulfuric acid solutions of ilmenite with insoluble metal sulfides, such as antimony sulfide or copper sulfide, enables one to operate with solutions of as high specific gravities as 1.550 to 1.570 (instead of 1.475 when glue is used), thereby increasing the cficlency of such subsequent steps in the process as crystallization and ccncentratim'z it has been observed that the filtration rate 01 the overfiow from the settling tank was rather slow in spite of its low content of unsettled coagulated matter, and that the precoat-cycles were short, necessitating frequent shut-downs for renewal of the precoat. The gain therefore in production experienced through the handling of a more concentrated solution in the settling tank was ofiset to some degree by the lowering of the camcity of the filter press used in the final clarification step.

We have now discovered a method by which it is possible to overcome the deficiencies of the metal sulfide clarification process.

Our method consists primarily in a special combination of metal sulfide and glue treatment in which the conjoint action of the metal sulfide and the glue provide unexpected improvements in the clarification of acid industrial liquors, especially sulfuric acid-ilmenite solutions.

Accordingly, the principal object of the present invention is the provision of a method whereby it will be possible to operate more eil'lciently than heretofore with titanium sulte'tesolutions of high specific gravity.

Our particular object is to provide a method of clarification whereby-the suspended insoluble coagulated material in the "overflow is rendered values; to increase the direct return to the discs,

tion reaction of the metal sulfide formed in the I itate a more rapid separatio more easily filterableand whereby frequent shutaceasec coagulation treatment, thereby increasing the recovery of the metal, e. g., animony, and to facilof the mud iroxn the liquid phase in the underfiow by improving the filterability thereof.

These and other objects will become apparent as the description of our invention proceeds.

We have discovered that if, in conjunction with the insoluble metal sulfide treatment, we add to the unclarified reduced sulfuric acid-ilmenite solution a small amount or an organic colloid which is coagulated by inorganic acid liquors, such as common glues, gelatins, albuminoids and proteins that the filterability of the "overfiow irom the settling system is improved to such a degree that the volume of filtrate from the filter press per preccat cycle is increased to about four times that of a similar "overflow" containing the same amount of suspended coagulated matter but setled with insoluble metal sulfide alone. We have also found that the separation by filtration of the solution from the coagulated residue in the "underflow from the settling system was improved by our novel treatment.

It was found that the addition of a small amount of glue in conjunction with the metal sulfide treatment did not noticeably afiect the rate and efiiciency of the gravitational settling of the coagulated residue, and it is in the unexpected improvement of the filterabllity of the overflow, brought about by the special conjoint action of the insoluble metal sulfide'and the glue that the principal novelty of our treatment resides.

' Improved washability of the filtered mud from the underflow was also observed as a consequence of the process of our invention.

We do not claim to know the real reason for the unexpected improvement in filtering qualities obtained with our novel treatment, but it is reasonable to believe that the improvementlles in the formation of floss of a size and mechanical structure conducive to the formation and maintenance of a strong and porous filter cake. We may, if desired, avail ourseli' of the use of filter aid in the filtration of the overflow from solutions treated according to our novel process.

In order that our improved process may be better understood by those skilled in the art we shall now by way of description oi actual operations explain the working oilour invention and the advantages derived therefrom.

To a mixture of one part by weight of ground ilmenlte and one and one half parts of 99 per cent sulfuric acid in. a digestion tank was added 9.1 per cent S1020: calculated on the total TiOz in the final batch, and a mixture or a slurry of to per cent washed underrlow solids in spent hydrolysis liquor representing '75 per cent of the mud obtained in the settling of a sulfate solution derived from a similar previous digestion of ilrnenite and mud. The antimony content of the recirculated mud represented per cent of the antimony required for the total batch. in

A reaction was caused to take place in kno manner, the reaction product was allowed to cool and the soluble compounds or titanium and iron were brought into solution by addition of water and weak acid solution circulated from the clari- 'flcation system; the solution was then reduced with metallic iron andpumped to the continuous cific gravity of insofar this temperature. The

Solution contained 0.6 g. p. 1. dissolved SbaOs.

ascasso j x I For the of clarification of the crude underfiow from the antimony sulfidesolutiona solution of sodium sulfide (8 per cent No.28) containing glue was added in a continuous stream to the solution as it was being pumped into the continuous clarification systems They amount of glue added was calculated to one part of dry glue ,to 10,000 parts by weight of solution. which amount of glue is only about one tenth of the amount required when coagulating with glue alone according to prior art. The sodium sul-.

fide was added in about 10 per cent excess of the calculated -molar equivalence of the antimony content.

In the ensuing reactionthe antimony was precipitated as antimony sulfide which together with the glue acted as a coagulant for the suspended unreacted colloidal mud.

The coagulated "mud" containing the antimony sulfide settled out while the supernatant liquor, the so-called overflow, still-analyzing Mil-0.5 (average about 0.1 g. p. l.) g. p. l. residue, was ed with 3-5 g. p. I. Hyfio (a diatomaceous filter aid) and then pumped to a filter press precoated with a diatomaceous earth, for example,

0. The rate of flow and the amount of filtered "overfiow obtained before blinding of the filter necessitated a renewalof the p'r ecoat were measured.

When operating exactly as described above,-

I before'blinding of the filter necessitated a shutdown for renewal of the precoat was'only about once-fourth to one-half of that obtained when coagulating with antimony and glue according to our novel method as described above. The rate of flow of filtrate when coagulating with antimony alone was also much slower than with conglue treatment containing'practically all of the settled "mud" and the antimony in the form of sulfide was processed for return to the digestion reaction, after dilution with spent acid from the hydrolysis department, one part by volume of underfiow to two parts ofdiluted spent acid,

the mu was settled and then .deliquored on acontinuous filter. The solution obtained from the settling and filtration of the mud was returned.

to the process in its entirety, whereas, as already described, per cent of the'washed "mu was recirculated'to the digestion for the'recovery of the antimony and digestible tltanium' values.

The 25 per cent of the antimony removed from circulation by bleeding the washed "mud slurry cent, when antimony alonewas used for coagulation as compared to 75 per cent when operating according to our novel method; The lower mud circulation constituted a corresponding loss of antimony and recoverable titanium in the mud! In the foregoing description of the treatment of I the'present, invention the coagulation of the residue was brought about'by the addition of a calculated amount of a sodium sulfide solution containing the required small amount ofglue. This procedure we have found to be very effective and convenient. It. is, however, not necessary I for a 1 successful operation with our -novel treatmentto introduce the sulfide and the small amount of glue as, one solution. Wehave found thatthe glue may be added separately at any time prior I to the filtration operation but not substantially before the sulfide is introduced.

- The following table sums up the results obtainable with clarification withglue'alone withantiv mony sulfide alone according to prior practice, 1 and with'antimony sulfide and glue coniointly accordin to our invention:

joint coagulation with antimony and glue.

' Used for Sp. gr. at Weight'ratio Production of ooagulation 60 0. Dry gluez'soln. 3:23:? TiO; in soln.

' v A Glue alone.. l. 415 1 1 0'00 s, 500 2B; SD20: alone--- 1. 550-1. 070- 4,ooo %ofA. Method Of inventlon C) Bb=0z+glue. 1. 550-1. 570 l 10, 000 8, Dr-16. 01X) E0 400% Of A.

1 Before blinding oi the filter slowed down the rate below an economical point.

excellent result obtained when coagulating with antimony and glue according to our invention is wholly unexpected in view of the fact that filtered overflow solution through increased filtrationxrate throughthe filter press and prolonged life of the filter press pro-coat, necessitating less frequent, shutdown'for renewal of the pro-coat, but that as a direct consequence of our treatment it became possible to operate with a greater amount'of recirculated mudlf This is, of course. an added advantage of our invention.

While we in the foregoing description of actual operations have confined ourselves to-the clarification of sulfuric acid solutions of ilmenite it should be understood that our novel clarification method is equally as useful in the clarification of sulfuric acid solutions derived from 'othertitaniferous ores and compounds. our method may. also be usedin the clarification of solutions containing the titanium in the form of, fore ple, chloride or fluoride. 'Our' method is adaptable for the clarification of solutions derived from the other one and compounds'than those containing titanium.

While we in the. description of the operation of our novel processhave given an amount of.- glue equal to about one part by weight of dry glue to'10,000 parts. or solution, it should be un-' derstood that we do not-wish tolimit ourselves to such an amount. Theiamount of glue used in our invention, although always very small, will a salt of a metal soluble in such liquor, the sulin our novel clarification treatment may be subject to variations without thereby deviating from the scope of the invention.

Having now described and explained in detail the working of our invention, what we claim is: 1. Process for the clarification of industrial acid liquors containing suspended matter which comprises forming, in situ, in such liquor an insoluble colloidal metal sulfide by reaction between fide of which is insoluble therein and at least a sufiicient amount of an inorganic sulfide also soluble in such liquor to prmipitate the metal of said salt as insoluble colloidal metal sulfide,

adding thereto at least about 1 part by weight 0 oi a coagulating organic colloid for every 10,000 parts by weight of liquor, and separating the settied residue containing the suspended matter, coagulated colloid and insoluble metal sulfide from the clarified supernatant liquor.

2. Process for the clarification of ilmenlte liquors which comprises forming, in situ, in such llguor an insoluble colloidal metal sulfide by reaction between a salt of a metal soluble in such liquor, the sulfide of which is insoluble therein and at least a sumclent amount of an inorganic sulfide also soluble in such liquor to precipitate the metal of said salt as insoluble colloidal metal sulfide, adding thereto at least about 1 part by weight or a coagulating organic colloid for every 35 10,000 parts by Weight of liquor, and separating the settled residue containing the suspended matter, coagnlated colloid and insoluble metal sulfate from the clarified supernatant liquor.

Eli

assasao 3, Process oi claim 2 wherein the metal compound forming the insoluble sulfide is a. com pound or antimony soluble in ilmenlte liquors.

4. Process of claim 2 wherein the soluble sul- :fide compound is an alkali metal sulfide.

5. Process according to claim 2 wherein the coagulating organic colloid is glue.

6. Process forthe clarification of ilmenite liquors containing suspended matter which comprises adding to an ilmenite liquor containing in solution a compound or antimony at least about 1 part by weight of glue for every 10,000 parts of liquor, and simultaneously adding sodium sulhole to form, in situ, insoluble colloidal antimony sulfide and separating the settled residue containing suspended matter, coagulated glue and insoluble antimony sulfide from the clarified ilmenite liquor.

7. Process for the clarification of industrial acid liquors containing suspended matter which comprises forming, in situ, in such liquor an insoluble colloidal metal sulfide by reaction between a salt oi a metal soluble in such liquor, the sulfide of which is insoluble therein, and at least a sufliclent amount of an inorganic sulfide also soluble in such liquor to precipitate the metal of said salt as insoluble colloidal metal sulfide, adding therete at least about 1 part by weight of a coagulating organic colloid selected from the group consisting of glues, gelatins, albuminoids and proteins for every 10,000 parts by weight of liquor, and separating thesettled residue containing the suspended matter, coagulated colloid and insoluble metal sulfide from the clarified supernatant liquor.

WALTER. G. MORAN. SANDFORD S. COLE. 

